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A tetranuclear nickel cluster isolated in multiple high-valent states

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Abstract

We report a series of high-valent tetranuclear nickel clusters isolated from the chemical oxidation of an all Ni(II) ([Ni4]) neutral cluster. Electrochemical analysis of [Ni4] reveals three reversible sequential oxidations at 0.248 V (1e), 0.678 V (1e), and 0.991 V (2e) vs. Fc/Fc+ corresponding to mono-, di-, and tetra-oxidized species, [Ni4]+, [Ni4]2+, [Ni4]4+, respectively. Using spectroscopic, crystallographic, magnetometric, and computational techniques, we assign the primary loci of oxidations to the Ni centers in each case, thus resulting in the isolation of the first tetranuclear all-Ni(III) cluster, [Ni4]4+.

Graphical abstract: A tetranuclear nickel cluster isolated in multiple high-valent states

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Supplementary files

Article information


Submitted
04 Mar 2020
Accepted
07 Apr 2020
First published
15 Apr 2020

Chem. Commun., 2020, Advance Article
Article type
Communication

A tetranuclear nickel cluster isolated in multiple high-valent states

S. I. Jacob, I. Douair, G. Wu, L. Maron and G. Ménard, Chem. Commun., 2020, Advance Article , DOI: 10.1039/D0CC01699C

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